Back to EveryPatent.com
United States Patent |
5,053,150
|
Emert
,   et al.
|
October 1, 1991
|
Polyepoxide modified adducts or reactants and oleaginous compositions
containing same
Abstract
A compound useful as a dispersant additive in oleaginous compositions
selected from fuels and lubricating oils comprising the reaction products
of:
(i) at least one intermediate adduct comprised of the reaction products of
(a) at least one polyepoxide, and
(b) at least one member selected from the group consisting of polyamines,
polyols, and amino alcohols; and
(ii) at least one of (a) hydrocarbyl substituted C.sub.4 -C.sub.10
dicarboxylic acid producing material or (b) an aldehyde and a hydrocarbyl
substituted hydroxy aromatic compound.
Also included is a process for preparing said compound and an oleaginous
composition containing said compound.
Inventors:
|
Emert; Jacob (Brooklyn, NY);
Lundberg; Robert D. (Bridgewater, NJ)
|
Assignee:
|
Exxon Chemical Patents Inc. (Linden, NJ)
|
Appl. No.:
|
625623 |
Filed:
|
December 4, 1990 |
Current U.S. Class: |
508/225; 548/520; 548/546 |
Intern'l Class: |
C10M 133/56; C10M 133/58 |
Field of Search: |
252/51.5 A,51.5 R
548/520,546
|
References Cited
U.S. Patent Documents
3078271 | Feb., 1963 | De Groote et al. | 260/247.
|
3188362 | Jun., 1965 | Delmonte | 260/835.
|
3272746 | Sep., 1966 | Le Suer et al. | 252/47.
|
3336241 | Aug., 1967 | Shokal | 260/2.
|
3367943 | Feb., 1968 | Miller | 260/326.
|
3373111 | Mar., 1968 | Le Suer et al. | 252/51.
|
3381022 | Apr., 1968 | Le Suer | 260/404.
|
3386953 | Jun., 1968 | Dunning et al. | 260/47.
|
3442808 | May., 1969 | Traise | 252/49.
|
3458530 | Jul., 1969 | Siegel et al. | 260/326.
|
3477990 | Nov., 1969 | Dante et al. | 260/47.
|
3539633 | Nov., 1970 | Plasek et al. | 260/570.
|
3579450 | May., 1971 | Le Suer et al. | 252/56.
|
3591598 | Jul., 1971 | Traise et al. | 260/296.
|
3630904 | Dec., 1971 | Musser et al. | 252/51.
|
3679632 | Jul., 1972 | Flowers et al. | 260/47.
|
3705109 | Dec., 1972 | Hausler et al. | 252/392.
|
3836470 | Sep., 1974 | Miller | 252/51.
|
3836471 | Sep., 1974 | Miller | 252/51.
|
3842010 | Oct., 1974 | Pappas et al. | 252/51.
|
3850826 | Nov., 1974 | de Vries | 252/51.
|
3859318 | Jan., 1975 | Le Suer | 260/410.
|
3879308 | Apr., 1975 | Miller | 252/56.
|
3957854 | May., 1976 | Miller | 260/482.
|
3957855 | May., 1976 | Miller | 260/482.
|
3962182 | Jun., 1976 | Steele | 260/47.
|
4097389 | Jun., 1978 | Andress, Jr. | 252/51.
|
4129508 | Dec., 1978 | Friihauf | 252/33.
|
4189450 | Feb., 1980 | Kempter et al. | 525/529.
|
4234435 | Nov., 1980 | Meinhardt et al. | 252/51.
|
4340455 | Jul., 1982 | Kempter et al. | 525/490.
|
4376849 | Mar., 1983 | Kempter et al. | 525/490.
|
4428849 | Dec., 1984 | Wisotsky | 252/33.
|
4455243 | Jun., 1984 | Liston | 252/49.
|
4482464 | Nov., 1984 | Karol et al. | 252/51.
|
4492642 | Dec., 1985 | Horodysky | 252/49.
|
4517104 | Jun., 1985 | Bloch et al. | 252/51.
|
4548724 | Oct., 1985 | Karol et al. | 252/51.
|
4579674 | Apr., 1986 | Schlicht | 252/51.
|
4617137 | Oct., 1986 | Plavac | 252/49.
|
4663064 | May., 1987 | Nalesnik et al. | 252/51.
|
4720350 | Jan., 1988 | Zoleski et al. | 252/51.
|
Foreign Patent Documents |
0317353 | May., 1989 | EP.
| |
Primary Examiner: Willis; Prince E.
Assistant Examiner: Johnson; Jerry D.
Attorney, Agent or Firm: Kapustij; M., Skula; E. R.
Parent Case Text
This is a continuation of application Ser. No. 161,899, filed Feb. 29,
1988, now abandoned.
Claims
What is claimed is:
1. A composition useful as dispersant additive for lubricating oil
compositions consisting essentially of reaction product of:
(i) at least one nitrogen containing adduct consisting essentially of
reaction product of
(a) at least one polyepoxide wherein the polyepoxide contains at least two
oxirane rings joined by a divalent organic moiety selected from the group
consisting of hydrocarbon moieties, and substituted hydrocarbon moieties;
and
(b) at least one polyamine wherein the polyamine contains at least two
reactive amino groups selected from primary amino groups and secondary
amino groups; and
(ii) at least one long chain hydrocarbyl substituted C.sub.4 -C.sub.10
dicarboxylic acid material, wherein said long chain substitutent is
derived from an olefin polymer having a number average molecular weight of
about 500 to about 6,000./
2. The composition of claim 1 wherein said long chain hydrocarbyl
substituted C.sub.4 -C.sub.10 dicarboxylic acid material is comprised of
reaction product of olefin polymer of C.sub.2 -C.sub.18 monoolefin having
a number average molecular weight of from about 500 to about 6,000, and
C.sub.4 -C.sub.10 monounsaturead dicarboxylic acid material.
3. The composition of claim 2 wherein said olefin polymer is
polyisobutylene.
4. The composition of claim 3 wherein said monounsaturated dicarboxylic
acid producing material is maleic anydride.
5. The composition of claim 4 wherein the number average molecular weight
of said polyisobutylene is from about 800 to about 2,500.
6. The composition of claim 1 wherein said reactive aminmo groups are
primary amino groups.
7. The composition of claim 6 wherein said polyamine contains in addition
to the primary amino groups at least one secondary amino group.
8. The composition of claim 1 wherein said polyamine is an aliphatic
saturated amine represented by the formula
##STR37##
wherein: R.sup.IV, R' and R''' are independently selected from the group
consisting of hydrogen, C.sub.1 l to C.sub.25 straight or branched chain
alkyl radicals, C.sub.1 to C.sub.12 alkoxy C.sub.2 to C.sub.6 alkylene
radicals, and C.sub.2 to C.sub.12 alkylamino C.sub.2 to C.sub.6 alkylene
radicals;
each s is independently selected from integers having a value of from 2 to
6; and
t is a number of 0 to 10, with the proviso that when t=0 at least one of
R.sup.IV, R''' or R' must be hydrogen such that there are at least two of
either primary or secondary amino groups.
9. The composition of claim 1 wherein said polyamine is selected from
poly(alkylene amines).
10. The composition of claim 1 wherein said polyamine is a poly(oxyalkylene
amine).
11. The composition of claim 1 wherein said hydrocarbon moiety is selected
from alkylene, cycloalkylene, alkenylene, arylene, aralkenylene, and
alkarylene moieties.
12. The composition of claim 1 wherein said polyepoxide contains at least
two oxirane rings wherein one oxirane ring carbon atom is bonded to two
hydrogen atoms.
13. The composition of claim 12 wherein one carbon atom in the second
oxirane ring is bonded to one hydrogen atom.
14. A lubricating oil composition comprising:
(A) a major amount of lubricating oil; and
(B) a minor amount of oil soluble dispersant compound consisting
essentially of reaction product of
(i) at least one nitrogen containing adduct consisting essentially of
reaction product of
(a) at least one polyepoxide wherein the polyepoxide contains at least two
oxirane rings joined by a divalent organic moiety selected from the group
consisting of hydrocarbon moieties, and substituted hydrocarbon moieties,
(b) at least one polyamine wherein the polyamine contains at least two
reactive amino groups selected from primary amino groups and secondary
amino groups; and
(ii) at least one long chain hydrocarbyl substituted C.sub.4 -c.sub.10
dicarboxylic acid material, wherein said long chain hydrocarbyl
substitutent is derived from an olefin polymer having a number average
molecular weight of about 500 to about 6,000.
15. The composition of claim 14 wherein said long chain hydrocarbyl
substituted C.sub.4 -C.sub.10 dicarboxylic acid material is comprised of
reaction product of olefin polymer of at least one C.sub.2 -C.sub.18
monoolefin having a number average molecular weight of about 500 to about
6,000, and C.sub.4 -c.sub.10 monounsaturated dicarboxylic acid material.
16. The composition of claim 15 wherein said olefin polymer is
polyisobutylene.
17. The composition of claim 16 wherein said monounsaturated dicarboxylic
acid material is maleic anhydride.
18. The composition of claim 17 wherein the number average molecular weight
of said polyisobutylene is from about 800 to about 2,500.
19. The composition of claim 14 wherein said reactive amino groups are
primary amino groups.
20. The composition of claim 19 wherein said polyamine contains in addition
to the primary amino groups at least one secondary amino group.
21. The composition of claim 14 wherein said polyamine is an aliphatic
saturated amine represented by the formula
##STR38##
wherein: R.sup.IV, R' and R''' are independently selected from the group
consisting of hydrogen, C.sub.1 to C.sub.25 straight and branched chain
alkyl radicals, C.sub.1 to C.sub.12 alkoxy C.sub.2 to C.sub.6 alkylene
radicals, and C.sub.1 to C.sub.12 alkylamino C.sub.2 to C.sub.6 alkylene
radicals;
each s is independently selected from integers having a value of from 2 to
6; and
t is a number of 0 to 10, with the proviso that when t=0 at least one of
R.sub.IV, R''' or R' must be hydrogen such that there are at least two of
either primary or secondary amino groups.
22. The composition of claim 14 wherein said polyamine is selected from
poly(alkylene amines).
23. The composition of claim 14 wherein said polyamine is a
poly(oxyalkylene amino).
24. The composition of claim 14 wherein said hydrocarbon moiety is selected
from alkylene, cycloalkylene, alkenylene, arylene, aralkenylene, and
alkarylene moieties.
25. The composition of claim 14 wherein said polyepoxide contains at least
two oxirane rings wherein one of the oxirane ring carbon atoms is bonded
to two hydrogen atoms.
26. The composition of claim 25 wherein one carbon atom in the second
oxirane ring is bonded to one hydrogen atom.
27. A process for preparing a composition useful as lubricating oil
dispersant additive consisting essentially of:
(i) forming reaction product consisting essentially of at least one
polyepoxide and at least one polygamies wherein the polyamine contains at
least two reactive amino groups selected from primary amino groups and
secondary amino groups; and
(ii) reacting said reaction product (i) with at least one long chain
hydrocarbyl substituted C.sub.4 -c.sub.10 dicarboxylic acid material, said
long chain hydrocarbyl substituted C.sub.4 -C.sub.10 acid material
consisting essentially of reaction product of olefin polymer of C.sub.2
-C.sub.18 monoolefin and having a number average molecular weight of from
about 500 to 6,000 and C.sub.4 -C.sub.10 monounsaturated dicarboxylic acid
material.
28. The process of claim 27 wherein said C.sub.4 -C.sub.10 monounsaturated
dicarboxylic acid material is maleic anhydride, which when reacted with
said olefin polymer forms one or more succinic anhydride moieties.
29. The process of claim 28 wherein there are present from about 0.7 to
about 2 succinic anhydride moieties per olefin polymer moiety in the said
long chain hydrocarbyl substituted C.sub.4 -C.sub.10 dicarboxylic acid
material, and wherein then umber average molecular weight of said olefin
polymer is from about 800 to about 2,500.
30. The process of claim 27 wherein said polyamine has from 2 to about 60
total carbon atoms and from about 2 to about 12 nitrogen atoms.
31. The process of claim 30 wherein said polyamine is an aliphatic
saturated amine having the formula:
##STR39##
wherein R.sup.IV, R'' and R''' are independently selected from the group
consisting of hydrogen, C.sub.1 to C.sub.25 straight or branched chain
alkyl radicals, C.sub.1 to C.sub.12 alkoxy C.sub.2 to C.sub.6 alkylene
radicals, and C.sub.1 to C.sub.12 alkylamino C.sub.2 to C.sub.6 alkylene
radicals; each s is the same or a different number of from 2 to 6; and t
is a number of from 0 to 10, with the proviso that when t =0 at least one
of R.sup.IV, R''' or R' must be H such that there are at least two of
either primary or secondary amino groups.
32. The process of claim 27 wherein said amine is selected from
poly(alkylene amines).
33. The process of claim 27 wherein said polyamine is a poly(oxyalkylene
amine).
34. The process of claim 27 wherein an excess amount of polyamine is used
over the stoichiometric amount of polyamine required to react with all of
the oxirane rings contained in said polyepoxide informing reaction product
(i).
35. The process of claim 27 wherein the provide from about 0.01to about 10
equivalents of epoxide moieties per one reactive amino moiety, said
reactive amino moiety being selected from the group consisting of primary
and secondary amino moieties.
36. The process of claim 35 wherein the polyepoxide reactant is used in an
amount sufficient to provide from about 0.1 to about 5 equivalents of
epoxide moieties per one reactive amino moiety.
37. The composition of claim 14 which contains a dispersant effective
amount of (B).
38. The composition of claim 37 which contains from about 0.01 to about 10
wt. % of (B).
39. The composition of claim 14 wherein said polyepoxide is a diepoxide.
40. A lubricating oil composition comprising:
(A) lubricating oil; and
(B) dispersant effective amount of oil soluble dispersant composition
consisting essentially of reaction product of
(i) reaction product consisting essentially of (a) polyepoxide wherein the
polyepoxide contains at least two oxirane rings joined by a divalent
organic moiety selected from the group consisting of hydrocarbon oieties,
and substituted hydrocarbon moieties reacted with (b) polyamine wherein
the polyamine contains at least two reactive amino groups selected from
primary amino groups and secondary amino groups, and
(ii) long chain hydrocarbyl substituted C.sub.4 -C.sub.10 dicarboxylic acid
or anhydride, wherein said long chain hydrocarbyl substitutent is derived
from an olefin polymer having a number average molecular weight of about
500 to about 6,000.
41. The composition of claim 40 wherein said long chain hydrocarbyl
substituted C.sub.4 -C.sub.10 dicarboxylic acid or anhydride consists
essentially of reaction product of olefin polymer having a number average
molecular weight of about 500 to about 6,000 and being derived from at
least one C.sub.2 -C.sub.18 monoolefin and a C.sub.4 -C.sub.10
monounsaturated dicarboxylic acid or anhydride.
42. The composition of claim 41 wherein said olefin polymer is comprised of
polyisobutene.
43. The composition of claim 41 wherein said monounsaturated dicarboxylic
acid material is maleic anhydride.
44. The composition of claim 43 wherein the number average molecular weight
of said olefin polymer is from about 800 to about 2,500.
45. The composition of claim 40 wherein said reactive amino groups are
primary amino groups.
46. The composition of claim 45 wherein said polyamine contains in addition
to the reactive primary amino groups at least one secondary amino group.
47. The composition of claim 40 wherein said polyamine is aliphatic a
saturated polyamine represented by the formula
##STR40##
wherein: R.sup.IV, R' and R''' are independently selected from the group
consisting of hydrogen, C.sub.1 to C.sub.25 straight and branched chain
alkyl radicals, C.sub.1 to C.sub.12 alkoxy C.sub.2 to C.sub.6 alkylene
radicals, and C.sub.1 to C.sub.12 alkylamino C.sub.2 to C.sub.6 alkylene
radicals;
each s is independently selected from integers having a value of from 2 to
6; and
t is a number from 0 to 10, with the proviso that when t=0 at least one or
R.sup.IV, R''' or R'must be hydrogen such that there are present at least
two of either primary or secondary amino groups.
48. The composition of claim 40 wherein said polyamine is selected from
poly(alkylene amines).
49. The composition of claim 40 wherein said polyamine is a
poly(oxyalkylene amine).
50. The composition of claim 40 wherein said hydrocarbon moiety is selected
from alkylene, cycloalkylene, alkenylkene, arylene, aralkenylene, and
alkarylene moieties.
51. The composition of claim 42 wherein said polyepoxide contains at least
two oxirane rings wherein one oxirane ring carbon atom is bonded to two
hydrogen atoms.
52. The composition of claim 51 wherein one carbon atom in the second
oxirane ring is bonded to one hydrogen atom.
53. A lubricating oil additive concentrate composition comprising:
(A) 20 to 98% by weight lubricating oil; and
(B) 2 to 80% by weight oil soluble dispersant composition consisting
essentially of reaction product of
(i) reaction product consisting essentially of
(a) at least one polyepoxide wherein the polyepoxide contains at least two
oxirane rings joined by a divalent organic moiety selected from the group
consisting of hydrocarbon moieties, and substituted hydrocarbon moieties,
and
(b) at least one polyamine wherein the polyamine contains at least two
reactive amino groups selected from primary amino groups and secondary
amino groups; and
(ii) at least one long chain hydrocarbyl substituted C.sub.4 -C.sub.10
dicarboxylic acid material, wherein said long chain substituent is derived
from an olefin polymer having a number average molecular weight of about
500 to about 6,000.
54. The composition of claim 53 wherein said long chain hydrocarbyl
substittued C.sub.4 -C.sub.10 dicarboxylic acid material is comprised of
reaction product of an olefin polymer having a number average molecular
weight of about 500 to about 6,000 and being derived from at least one
C.sub.2 -C.sub.18 monoolefin, and C.sub.4 -C.sub.10 monounsaturated
dicarboxylic acid material.
55. The composition of claim 54 wherein said olefin polymer is
polyisobutene.
56. The composition of claim 54 wherein said monounsaturated dicarboxylic
acid material is maleic anhydride.
57. The composition of claim 56 wherein the number average molecular weight
of said polyisobutene is from about 800 to about 2,500.
58. The composition of claim 53 wherein said reactive amino groups are
primary amino groups.
59. The composition of claim 58 wherein said polyamine contains in addition
to the reactive primary amino groups at least one secondary amino group.
60. The composition of claim 53 wherein said polyamine is an aliphatic
saturated amine represented by the formula
##STR41##
wherein: R.sup.IV, R' and R''' are independently selected from the group
consisting of hydrogen, C.sub.1 to C.sub.25 straight or branched chain
alkyl radicals, C.sub.1 to C.sub.12 alkoxy C.sub.2 to C.sub.6 alkylene
radicals, and C.sub.1 to C.sub.12 alkylamino C.sub.2 to C.sub.6 alkylene
radicals;
each s is independently selected from integers having a value of from 2 to
6; and
t is a number of 0 to 10, with the proviso that when t=0 at least one of
R.sup.IV, R''' or R'must be hydrogen such that there are at least two of
either primary or secondary amino groups.
61. The composition of claim 53 wherein said polyamine is selected from
poly(alkyolene mines).
62. The composition of claim 53 wherein said polyamine is a
poly(oxyalkylene amine).
63. The composition of claim 53 wherein said hydrocarbon moiety is selected
from alkylene, cycloalkylene, alkenylene, arylene, aralkenylene, and
alkarylene moieties.
64. The composition of claim 53 wherein said polyepoxide contains at least
two oxirane rings wherein one oxirane ring carbon atom is bonded to two
hydrogen atoms.
65. The composition of claim 64 wherein one carbon atom in the second
oxirane ring is bonded to one hydrogen atom.
Description
FIELD OF THE INVENTION
This invention relates to oil soluble dispersant additives useful in
oleaginous compositions selected from fuel and lubricating oil
compositions, including concentrates containing said additives, and
methods for their manufacture and use. The dispersant additives are
polyepoxide adducts which have been prepared by first reacting a
polyepoxide with a polyamine, a polyol or an amino alcohol to form an
intermediate adduct, whereafter the intermediate adduct is reacted with at
least one of (a) a dicarboxylic acid, anhydride, ester, etc. which in turn
has been substituted with a high molecular weight hydrocarbon group or (b)
an aldehyde and a hydrocarbyl substituted hydroxy aromatic compound. The
high molecular weight hydrocarbon group has a number average molecular
weight (M.sub.n) of about 500 to about 6,000.
BACKGROUND OF THE INVENTION
Multigrade lubricating oils typically are identified by two numbers such as
1OW30, 5W30 etc. The first number in the multigrade designation is
associated with a maximum low temperature (e.g.-20.degree. C.) viscosity
requirement for that multigrade oil as measured typically by a cold
cranking simulator (CCS) under high shear, while the second number in the
multigrade designation is associated with a minimum high temperature (e.g.
100.degree. C.) viscosity requirement. Thus, each particular multigrade
oil must simultaneously meet both strict low and high temperature
viscosity requirements in order to qualify for a given multigrade oil
designation. Such requirements are set e.g., by ASTM specifications. By
"low temperature" as used herein is meant temperatures of typically from
about -30 to about -5.degree. C. By "high temperature" as used herein is
meant temperatures of typically at least about 100.degree. C.
The minimum high temperature viscosity requirement, e.g. at 100.degree. C.,
is intended to prevent the oil from thinning out too much during engine
operation which can lead to excessive wear and increased oil consumption.
The maximum low temperature viscosity requirement is intended to
facilitate engine starting in cold weather and to ensure pumpability,
i.e., the cold oil should readily flow or slump into the well for the oil
pump, otherwise the engine can be damaged due to insufficient lubrication.
In formulating an oil which efficiently meets both low and high temperature
viscosity requirements, the formulator may use a single oil of desired
viscosity or a blend of two lubricating oils of different viscosities, in
conjunction with manipulating the identity and amount of additives that
must be present to achieve the overall target properties of a particular
multigrade oil including its viscosity requirements.
The natural viscosity characteristic of a lubricating oil is typically
expressed by the neutral number of the oil (e.g. S150N) with a higher
neutral number being associated with a higher natural viscosity at a given
temperature. In some instances the formulator will find it desirable to
blend oils of two different neutral numbers, and hence viscosities, to
achieve an oil having a viscosity intermediate between the viscosity of
the components of the oil blend. Thus, the neutral number designation
provides the formulator with a simple way to achieve a desired base oil of
predictable viscosity. Unfortunately, merely blending oils of different
viscosity characteristics does not enable the formulator to meet the low
and high temperature viscosity requirements of multigrade oils. The
formulator's primary tool for achieving this goal is an additive
conventionally referred to as a viscosity index improver (i.e., V.I.
improver).
The V. I. improver is conventionally an oil-soluble long chain polymer. The
large size of these polymers enables them to significantly increase
Kinematic viscosities of base oils even at low concentrations. However,
because solutions of high polymers are non-Newtonian they tend to give
lower viscosities than expected in a high shear environment due to the
alignment of the polymer. Consequently, V.I. improvers impact (i.e.,
increase) the low temperature (high shear) viscosities (i.e. CCS
viscosity) of the base oil to a lesser extent than they do the high
temperature (low shear) viscosities.
The a foresaid viscosity requirements for a multigrade oil can therefore be
viewed as being increasingly antagonistic at increasingly higher levels of
V.I. improver. For example, if a large quantity of V.I. improver is used
in order to obtain high viscosity at high temperatures, the oil may now
exceed the low temperature requirement. In another example, the formulator
may be able to readily meet the requirement for a 1OW30 oil but not a 5W30
oil, with a particular ad-pack (additive package) and base oil. Under
these circumstances the formulator may attempt to lower the viscosity of
the base oil, such as by increasing the proportion of low viscosity oil in
a blend, to compensate for the low temperature viscosity increase induced
by the V.I. improver, in order to meet the desired low and high
temperature viscosity requirements. However, increasing the proportion of
low viscosity oils in a blend can in turn lead to a new set of limitations
on the formulator, as lower viscosity base oils are considerably less
desirable in diesel engine use than the heavier, more viscous oils. In
addition the added volatility of lower viscosity base oil can present a
practical problem.
Further complicating the formulator's task is the effect that dispersant
additives can have on the viscosity characteristics of multigrade oils.
Dispersants are frequently present in quality oils such as multigrade
oils, together with the V.I. improver. The primary function of a
dispersant is to maintain oil insolubles, resulting from oxidation during
use, in suspension in the oil thus preventing sludge flocculation and
precipitation. Consequently, the amount of dispersant employed is dictated
and controlled by the effectiveness of the material for achieving its
dispersant function. A high quality 10W30 commercial oil might contain
from two to four times as much dispersant as V.I. improver (as measured by
the respective dispersant and V.I. improver active ingredients). In
addition to dispersancy, conventional dispersants can also increase the
low and high temperature viscosity characteristics of a base oil simply by
virtue of their polymeric nature. In contrast to the V.I. improver, the
dispersant molecule is much smaller. Consequently, the dispersant is much
less shear sensitive, thereby contributing more to the low temperature CCS
viscosity (relative to its contribution to the high temperature viscosity
of the base oil) than a V.I. improver. Moreover, the smaller dispersant
molecule contributes much less to the high temperature viscosity of the
base oil than the V.I. improver. Thus, the magnitude of the low
temperature viscosity increase induced by the dispersant can exceed the
low temperature viscosity increase induced by the V.I. improver without
the benefit of a proportionately greater increase in high temperature
viscosity as obtained from a V.I. improver. Consequently, as the
dispersant induced low temperature viscosity increase causes the low
temperature viscosity of the oil to approach the maximum low temperature
viscosity limit, the more difficult it is to introduce a sufficient amount
of V.I. improver effective to meet the high temperature viscosity
requirement and still meet the low temperature viscosity requirement. The
formulator is thereby once again forced to shift to the undesirable
expedient of using higher proportions of low viscosity oil to permit
addition of the requisite amount of V.I. improver without exceeding the
low temperature viscosity limit.
In accordance with the present invention, dispersants are provided which
have been found to possess inherent characteristics such that they
contribute considerably less to low temperature viscosity increases than
dispersants of the prior art while achieving similar high temperature
viscosity increases. Moreover, as the concentration of dispersant in the
base oil is increased, this beneficial low temperature viscosity effect
becomes increasingly more pronounced relative to conventional dispersants.
This advantage is especially significant for high quality heavy duty
diesel oils which typically require high concentrations of dispersant
additive. Furthermore, these improved viscosity properties facilitate the
use of V.I. improvers in forming multigrade oils spanning a wider
viscosity requirement range, such as 5W30 oils, due to the overall effect
of lower viscosity increase at low temperatures while maintaining the
desired viscosity at high temperatures as compared to the other
dispersants. More significantly, these viscometric properties also permit
the use of higher viscosity base stocks with attendant advantages in
engine performance. Furthermore, the utilization of the dispersant
additives of the instant invention allows a reduction in the amount of
V.I. improvers required.
The materials of this invention are thus an improvement over conventional
dispersants because of their effectiveness as dispersants coupled with
enhanced low temperature viscometric properties These materials are
particularly useful with V.I. improvers in formulating multigrade oils.
SUMMARY OF THE INVENTION
The present invention is directed to oil soluble dispersant additives
useful in oleaginous compositions selected from fuels and lubricating oils
comprising the reaction products of:
(i) at least one intermediate adduct comprised of the reaction products of
(a) at least one polyepoxide, and
(b) at least one member selected from the group consisting of polyamines,
polyols, and amino alcohols; and
(ii) at least one of (a) a hydrocarbyl substituted C.sub.4 -C.sub.10
dicarboxylic acid producing material or (b) an aldehyde and a hydrocarbyl
substituted hydroxy aromatic compound.
The intermediate adduct (i) is first performed and this performed
intermediate adduct is subsequently reacted with (ii).
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention there are provided oil soluble
dispersant compositions. These dispersants exhibit a high temperature to
low temperature viscosity balance or ratio which is more favorable than
that of conventional dispersant materials. That is to say the instant
dispersant materials possess inherent characteristics such that they
contribute considerably less to low temperature viscosity increase than
conventional dispersants while increasing the contribution to the high
temperature viscosity increase They also exhibit enhanced and improved
dispersancy characteristics. This is believed to be due, inter alia, to
the presence of the hydroxyl groups formed as a result of the ring opening
of the oxirane rings in their reaction with the reactive amino groups of
the polyamine or hydroxyl groups of the polyol in the formation of the
intermediate adduct (i).
The dispersant materials of the instant invention comprise the reaction
products of
(i) at least one intermediate adduct comprised of the reaction products of
(a) at least one polyepoxide, and
(b) at least one member selected from the group consisting of polyamines,
polyols, and amino alcohols; and
(ii) at least one of (a) a hydrocarbyl substituted C.sub.4 -C.sub.10
dicarboxylic acid producing material or (b) an aldehyde and a hydrocarbyl
substituted hydroxy aromatic compound.
The reaction product (i), also referred to in the specification and
appended claims as the intermediate adduct, is then reacted with (ii)(a)
or (ii)(b), with (ii) (a) being referred to in the specification and
appended claims as an acylating agent or material, to form the adduct or
dispersant of the present invention. If (i)(b) is a polyamine then it
contains at least two reactive amino groups, one of said amino groups
being a primary amino group and the other reactive amino group being a
primary amino group or a secondary amino group.
In a preferred embodiment of the instant invention (i)(b) is a polyamine,
and in the following discussion concerning the reaction between (i)(a) and
(i)(b) to form the intermediate adduct, (i)(b) will be assumed to be such
a polyamine.
In another preferred embodiment (i)(b) is a polyamine and (ii) is (a).
For purposes of illustration and exemplification only the reaction between
one mole of a polyepoxide, i.e., a diepoxide, and two moles of a polyamine
such as tetraethylene pentamine (TEPA), to form the intermediate adduct is
believed to be represented by the following reaction scheme:
##STR1##
It is to be understood that if more than one molecule of the diepoxide and
more than 2 molecules of the polyamine are incorporated into the resultant
product, said product may be oligmeric in character. Thus for example, if
more than one mole of the diepoxide of Equation 1 is reacted with more
than 2 moles of the polyamine of Equation 2 the resultant product may be
represented by the following structural formula
##STR2##
where h is a number obtained by subtracting one from the number of moles
of diepoxide and is at least one.
This intermediate adduct is then reacted with (ii)(a) or (ii)(b) such as
polyisobutenyl succinic anhydride, i.e., 2 moles of
##STR3##
where PIB represents polyisobutylene having a number average molecular
weight of from about 500 to about 6,000, to form the dispersant of the
instant invention, i.e., a mixture of amides, imides and esters, e.g.,
##STR4##
ACID PRODUCING MATERIAL
The acylating agents (ii)(a) may be reacted with the polyepoxide-polyamine,
polyepoxide-polyol, and/or polyepoxide-amino alcohol intermediate adducts
to form the dispersant additives of the instant invention are dicarboxylic
acid materials, e.g., acid, anhydride or ester materials, which are
substituted with a long chain hydrocarbyl group, generally a polyolefin,
and which contain typically an average of at least about 0.7, usefully
from about 0.7-2.0 (e.g., 0.9-1.6) preferably about 1.0-1.3 (e.g. 1.1-1.2)
moles, per mole of hydrocarbyl, of a C.sub.4 to C.sub.10 dicarboxylic
acid, anhydride or ester thereof, such as succinic acid, succinic
anhydride, dimethyl methylsuccinate, etc., and mixtures thereof.
The hydrocarbyl substituted dicarboxylic acid materials, as well as methods
for their preparation, are well known in the art and are amply described
in the patent literature. They may be obtained, for example, by the Ene
reaction between a polyolefin and an alpha-beta unsaturated C.sub.4 to C10
dicarboxylic acid, anhydride or ester thereof, such as fumaric acid,
itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl
fumarate, etc.
The hydrocarbyl substituted dicarboxylic acid materials function as
acylating agents for the polyepoxide intermediate adduct.
Preferred olefin polymers for reaction with the unsaturated dicarboxylic
acid, anhydride, or ester are polymers comprising a major molar amount of
C.sub.2 to C.sub.18, e.g. C.sub.2 to C.sub.5, monoolefin. Such olefins
include ethylene, propylene, butylene, isobutylene, pentene, octene-1,
styrene, etc. The polymers can be homopolymers such as polyisobutylene, as
well as copolymers of two or more of such olefins such as copolymers of:
ethylene and propylene; butylene and isobutylene; propylene and
isobutylene; etc. Other copolymers include those in which a minor molar
amount of the copolymer monomers, e.g., 1 to 10 mole %, is a C.sub.4 to
C.sub.18 non-conjugated diolefin, e.g., a copolymer of isobutylene and
butadiene; or a copolymer of ethylene, propylene and 1,4-hexadiene; etc.
In some cases the olefin polymer may be completely saturated, for example
an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using
hydrogen as a moderator to control molecular weight.
The olefin polymers will usually have number average molecular weights
(M.sub.n) within the range of about 500 and about 6000, e.g. 700 to 3000,
preferably between about 800 and about 2500, e.g., 850 to 1,000. An
especially useful starting material for a disspersant additive made in
accordance with this invention is polyisobutylene.
Processes for reacting the olefin polymer with the C.sub.4 -C.sub.10
unsaturated dicarboxylic acid, anhydride or ester are known in the art.
For example, the olefin polymer and the dicarboxylic acid material may be
simply heated together as disclosed in U.S. Pat. Nos. 3,361,673 and
3,401,118 to cause a thermal "ene" reaction to take place. Alternatively,
the olefin polymer can be first halogenated, for example, chlorinated or
brominated to about 1 to 8 wt. %, preferably 3 to 7 wt. % chlorine or
bromine, based on the weight of polymer, by passing the chlorine or
bromine through the polyolefin at a temperature of 25 to 160.degree. C,
e.g., 120.degree. C., for about 0.5 to 10, preferably 1 to 7 hours. The
halogenated polymer may then be reacted with sufficient unsaturated acid
or anhydride at 100 to 250.degree. C., usually about 180 to 220.degree.
C., for about 0.5 to 10 hours, e.g. 3 to 8 hours, so the product obtained
will contain an average of about 0.1 to 2.0 moles, preferably 1.1 to 1.3
moles, e.g., 1.2 moles, of the unsaturated acid per mole of the
halogenated polymer. Processes of this general type are taught in U.S.
Pat. Nos. 3,087,436; 3,172,892; 3,272,746 and others.
Alternatively, the olefin polymer and the unsaturated acid material are
mixed and heated while adding chlorine to the hot material. Processes of
this type are disclosed in U.S. Pat. Nos. 3,215,707; 3,231,587; 3,912,764;
4,110,349; 4,234,435; and in U.K. 1,440,219.
By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g.
polyisobutylene, will normally react with the dicarboxylic acid material.
Upon carrying out a thermal reaction without the use of halogen or a
catalyst, then usually only about 50 to 85 wt. % of the polyisobutylene
will react. Chlorination helps increase the reactivity. For convenience,
all of the aforesaid functionality ratios of dicarboxylic acid producing
units to polyolefin, e.g. 1.0 to 2.0, etc. are based upon the total amount
of polyolefin, that is, the total of both the reacted and unreacted
polyolefin, present in the resulting product formed in the aforesaid
reactions.
POLYAMINES
Amine compounds useful as reactants with the polyepoxides to form the
polyepoxide-polyamine intermediate adduct are those containing at least
two reactive amino groups, i.e., primary and secondary amino groups. They
include polyalkylene polyamines, of about 2 to 60 (e.g. 2 to 30) ,
preferably 2 to 40, (e.g. 3 to 20) total carbon atoms and about 1 to 12
(e.g., 2 to 9) , preferably 3 to 12, and most preferably 3 to 9 nitrogen
atoms in the molecule. These amines may be hydrocarbyl amines or may be
hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy
groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy
amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are
particularly useful. Such amines should be capable of reacting with the
acid or anhydride groups of the hydrocarbyl substituted dicarboxylic acid
moiety and with the oxirane rings of the polyepoxide moiety through the
amino functionality or a substituent group reactive functionality. Since
tertiary amines are generally unreactive with anhydrides and oxirane
rings, it is desirable to have at least two primary and/or secondary amino
groups on the amine. It is preferred that the amine contain at least one
primary amino group, to facilitate reaction with the polyepoxide.
Preferred amines are aliphatic saturated amines, including those of the
general formulae:
##STR5##
wherein R.sup.IV, R', R'', and R''' are independently selected from the
group consisting of hydrogen; C.sub.1 to C.sub.25 straight or branched
chain alkyl radicals; C.sub.1 to C.sub.12 alkoxy C.sub.2 to C.sub.6
alkylene radicals; C.sub.2 to C12 hydroxy amino alkylene radicals; and
C.sub.1 to C.sub.12 alkylamino C.sub.2 to C.sub.6 alkylene radicals; and
wherein R'' and R''' can additionally comprise a moiety of the formula
##STR6##
wherein R' is as defined above, and wherein each s and s' can be the same
or a different number of from 2 to 6, preferably 2 to 4; and t and t' can
be the same or different and are each numbers of typically from 0 to 10,
preferably about 2 to 7, most preferably about 3 to 7, with the proviso
that t +t' is not greater than 10. To assure a facile reaction it is
preferred that R.sup.IV, R'' R''', (s), (s'), (t) and (t') be selected in
a manner sufficient to provide the compounds of formula Ia with typically
at least two primary and/or secondary amino groups. This can be achieved
by selecting at least one of said RIV, R", or R''' groups to be hydrogen
or by letting (t) in formula Ia be at least one when R''' is H or when the
(Ib) moiety possesses a secondary amino group. The most preferred amines
of the above formulas are represented by formula Ia and contain at least
two primary amino groups and at least one, and preferably at least three,
secondary amino groups.
Non-limiting examples of suitable amine compounds include:
1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;
1,6-diaminohexane; polyethylene amines such as diethylene triamine;
triethylene tetramine; tetraethylene pentamine; polypropylene amines such
as 1,2-propylene diamine; di-(1,2-propylene) triamine; di-(1,3-propylene)
triamine; N, N'-dimethyl- 1, 3 -diaminopropane; N, N'-di-(2-aminoethyl)
ethylene diamine; N,N'-di(2-hyudroxyethyl)-1,3propylene diamine;
N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);
diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, and
tri-tallow amines; amino morpholines such as N-(3 aminopropyl) morpholine;
and mixtures thereof.
Other useful amine compounds include: alicyclic diamines such as
1,4-di(aminoethyl) cyclohexane, and N-aminoalkyl piperazines of the
general formula
##STR7##
wherein p.sub.1 and p.sub.2 are the same or different and are each
integers of from 1 to 4, and n.sub.1, n.sub.2 and n.sub.3 are the same or
different and are each integers of from 1 to 3.
Commercial mixtures of amine compounds may advantageously be used. For
example, one process for preparing alkylene amines involves the reaction
of an alkylene dihalide (such as ethylene dichloride or propylene
dichloride) with ammonia, which results in a complex mixture of alkylene
amines wherein pairs of nitrogens are joined by alkylene groups, forming
such compounds as diethylene triamine, triethylenetetramine, tetraethylene
pentamine and corresponding piperazines. Low cost poly(ethyleneamine)
compounds averaging about 5 to 7 nitrogen atoms per molecule are available
commercially under trade names such as "Polyamine H", "Polyamine 400",
"Dow Polyamine E-100", etc.
Useful amines also include polyoxyalkylene polyamines such as those of the
formulae:
##STR8##
where m has a value of about 3 to 70 and preferably 10 to 35; and where n
has a value of about 1 to 40, with the provision that the sum of all the
n's is from about 3 to about 70, and preferably from about 6 to about 35,
and R.sup.V is a substituted saturated hydrocarbon radical of up to 10
carbon atoms, wherein the number of substituents on the R.sup.V group is
from 3 to 6, and "a" is a number from 3 to 6 which represents the number
of substituents on R.sup.V. The alkylene groups in either formula (III) or
(IV) may be straight or branched chains containing about 2 to 7, and
preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas (III) or (IV) above, preferably
polyoxyalkylene diamines and polyoxyalkylene triamines, may have number
average molecular weights ranging from about 200 to about 4000 and
preferably from about 400 to about 2000. The preferred polyoxyalkylene
polyamines include the polyoxyethylene and polyoxypropylene diamines and
the polyoxypropylene triamines having average molecular weights ranging
from about 200 to 2000. The polyoxyalkylene polyamines are commercially
available and may be obtained, for example, from the Jefferson Chemical
Company, Inc. under the trade name "Jeffamines D-230, D-400, D-1000,
D-2000, T-403", etc.
The polyamine is readily reacted with the polyepoxide, with or without a
catalyst, simply by heating a mixture of the polyepoxide and polyamine in
a reaction vessel at a temperature of about -20.degree. C. to about
200.degree. C., more preferably to a temperature of about 0.degree. C. to
about 180.degree. C., and most preferably at about 30.degree. C. to about
160.degree. C., for a sufficient period of time to effect reaction. A
solvent for the polyepoxide, polyamine and/or intermediate adduct can be
employed to control viscosity and/or reaction rates.
Catalysts use fuel in the promotion of the above-identified
polyepoxide-polyamine reactions are selected from the group consisting of
stannous octanoate, stannous hexanoate, stannous oxalate, tetrabutyl
titanate, a variety of metal organic based catalyst acid catalysts and
amine catalysts, as described on page 266, and forward in a book chapter
authored by R. D. Lundberg and E. F. Cox entitled, "Kinetics and
Mechanisms of Polymerization: Ring Opening Polymerization", edited by
Frisch and Reegen, published by Marcel Dekker in 1969, wherein stannous
octanoate is an especially preferred catalyst. The catalyst is added to
the reaction mixture at a concentration level of about 50 to about 10,000
parts of catalyst per one million parts by weight of the total reaction
mixture.
POLYOL
In another aspect of the invention the polyepoxide intermediate adducts are
prepared by reacting the polyepoxides with a polyol instead of with a
polyamine
Suitable polyol compounds which can be used include aliphatic polyhydric
alcohols containing up to about 100 carbon atoms and about 2 to about 10
hydroxyl groups. These alcohols can be quite diverse in structure and
chemical composition, for example, they can be substituted or
unsubstituted, hindered or unhindered, branched chain or straight chain,
etc. as desired. Typical alcohols are alkylene glycols such as ethylene
glycol, propylene glycol, trimethylene glycol, butylene glycol, and
polyglycols such as diethylene glycol, triethylene glycol, tetraethylene
glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol,
tributylene glycol, and other alkylene glycols and polyalkylene glycols in
which the alkylene radical contains from two to about eight carbon atoms.
Other useful polyhydric alcohols include glycerol, monomethyl ether of
glycerol, pentaerythritol, dipentaerythritol, tripentaerythritol,
9,10-dihydroxystearic acid, the ethyl ester of 9, 10-dihydroxystearic
acid, 3-chloro-1,2-propanediol, 1,2-butanediol, 1,4-butanediol,
2,3-hexanediol, pinacol, tetrahydroxy pentane, erythritol, arabitol,
sorbitol, mannitol, 1,2-cyclohexanediol, 1,4-cyclohexanediol,
1,4-(2-hydroxyethyl)-cyclohexane, 1,4-dihydroxyethyl-2-nirobutane,
1,4-di-(2-hydroxyethyl)-benzene, and the carbohydrates such as glucose,
mannose, glyceraldehyde, galactose, and the like.
Included within the group of aliphatic alcohols are those alkane polyols
which contain ether groups such as polyethylene oxide repeating units, as
well as those polyhydric alcohols containing at least three hydroxyl
groups, at least one of which has been esterified with a mono-carboxylic
acid having from eight to about 30 carbon atoms such as octanoic acid,
oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oil
acid. Examples of such partially esterified polyhydric alcohols are the
mono-oleate of sorbitol, the mono-oleate of glycerol, the monostearate of
glycerol, the di-stearate of sorbitol, and the di-dodecanoate of
erythritol.
A preferred class of intermediate adducts are those prepared from aliphatic
alcohols containing up to 20 carbon atoms, and especially those containing
three to 15 carbon atoms. This class of alcohols includes glycerol,
erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol,
gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-heptanediol,
2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol,
2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, 2,2,6,6-tetrakis
(hydroxymethyl) -cyclohexanol, 1,10-decanediol, and the like. The adducts
repared from aliphatic alcohols containing at least three hydroxyl groups
and up to fifteen carbon atoms are particularly preferred.
An especially preferred class of polyhydric alcohols for preparing the
polyepoxide adducts used as intermediate materials or dispersant
precursors in the present invention are the polyhydric alkanols containing
three to 15, especially three to six carbon atoms and having at least
three hydroxyl groups. Such alcohols are exemplified in the above
specifically identified alcohols and are represented by glycerol,
erythritol, pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol, and
tetrahydroxy pentane and the like.
The polyol is readily reacted with the polyepoxide by heating a mixture of
the polyol and polyepoxide in a reaction vessel at a temperature of about
-20.degree. C. to about 200.degree. C., more preferably to a temperature
of about 0.degree. C. to about 180.degree. C., and most preferable at
about 30.degree. C. to about 160.degree. C., for a sufficient period of
time to effect reaction. Optionally, a solvent for the polyepoxide, polyol
and/or the resulting adduct may be employed to control viscosity and/or
the reaction rates.
Catalysts useful in the promotion of the polyepoxide-polyol reactions are
the base catalysts, e.g., OH .sup.--, tertiary amines, etc. The catalyst
may be added to the reaction mixture at a concentration level of from
about 50 to about 10,000 parts of catalyst per one million parts by weight
of total reaction mixture.
AMINO ALCOHOL
In a manner analogous to that described for the polyepoxide-polyamine
reaction and for the polyepoxide-polyol reaction, the polyepoxide can be
reacted with an amino alcohol to form an intermediate adduct which can be
further reacted with an acylating agent to form the dispersants of this
invention.
Suitable amino alcohol compounds which can be reacted with the polyepoxide
include those containing up to about 50 total carbon atoms and preferably
up to about 10 total carbon atoms, from to about 5 nitrogen atoms,
preferably from 1 to 3 nitrogen atoms, and from 1 to about 15 hydroxyl
groups, preferably from about 1 to 5 hydroxyl groups. Some illustrative
non-limiting examples of the amino alcohols include ethanol amine,
triethanol amine, di-(2-hydroxyethyl)amine, tri-(3-hydroxypropyl)amine,
and N,N'-di-(hydroxyethyl)ethylenediamine. Preferred amino alcohols
include the 2,2-disubstituted-2-amino-1-alkanols having from two to three
hydroxy groups and containing a total of 4 to 8 carbon atoms. These amino
alcohols can be represented by the formula:
##STR9##
wherein Z is independently hydrogen, alkyl or hydroxyalkyl group with the
alkyl groups having from 1 to 3 carbon atoms wherein at least one, and
preferably both, of the X substituents is a hydroxyalkyl group of the
structure --(CH.sub.2).sub.n OH, n being 1 to 3. Examples of such amino
alcohols include 2-amino-2-methyl-1,3-propanediol; 2-amino-2
-ethyl-1,3-propanediol; and 2-amino-2-(hydroxymethyl) -1,3-propanediol the
latter also being known as THAM or tris(hydroxymethyl) amino methane THAM
is particularly preferred because of its effectiveness, availability and
low cost.
The amino alcohol is readily reacted with the polyepoxide by heating a
mixture of the polyepoxide and amino alcohol in a reaction vessel at a
temperature of about -20.degree. C. to about 200.degree. C., more
preferably at temperature of about 0.degree. C. to about 180.degree. C.,
and most preferably at about 30.degree. C. to about 160.degree. C., for a
sufficient period of time to effect reaction. Optionally, a solvent for
the polyepoxide, amino alcohol and/or the reaction product may be used to
control viscosity and/or the reaction rates.
Catalysts useful in the promotion of the polyepoxide-amino alcohol
reactions are the same as those which are useful in connection with the
polyepoxide-polyamine and polyepoxide-polyol reactions, and corresponding
amounts of catalysts may be employed.
HYDROCARBYL SUBSTITUTED HYDROXY AROMATIC COMPOUNDS AND ALDEHYDES
In another embodiment of the present invention the instant dispersants are
comprised of the reaction products of the intermediate adduct (i),
preferably one comprised of the reaction products of at least one
polyepoxide and at least one polyamine, and (ii)(b), i.e., an aldehyde and
a hydrocarbyl substituted hydroxy aromatic compound.
The hydrocarbyl substituted hydroxy aromatic compounds include those
compounds having the formula
##STR10##
wherein Ar represents
##STR11##
wherein q is or 2, R.sup.21 is a long chain hydrocarbon, R.sup.20 is a
hydrocarbon or substituted hydrocarbon radical having from 1 to about 3
carbon atoms or a halogen radical such as the bromide or chloride radical
y is an integer from 1 to 2, x is an integer from 0 to 2, and z is an
integer from 1 to 2.
Illustrative of such Ar groups are phenylene, biphenylene, naphthylene and
the like.
The preferred long chain hydrocarbon substituents are olefin polymers
comprising a major molar amount of C.sub.2 to C.sub.8, e.g. C.sub.2 to
C.sub.5 monoolefin. Such olefins include ethylene, propylene, butylene,
pentene, octene-1, styrene, etc. The polymers can be homopolymers such as
polyisobutylene, as well as copolymers of two or more of such olefins such
as copolymers of: ethylene and propylene; butylene and isobutylene;
propylene and isobutylene; etc. Other copolymers include those in which a
minor molar amount of other monomers are present, e.g., a copolymer of
isobutylene and butadiene; or a copolymer of ethylene, propylene and
1,4-hexadiene; etc.
In some cases, the olefin polymer may be completely saturated, for example
an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using
hydrogen as a moderator to control molecular weight.
The olefin polymers will usually have a number average molecular weight
(M.sub.n) within the range of about 700 to about 10,000, more usually
between about 700 and about 5,000. Particularly useful olefin polymers
have number average molecular weight within the range of about 700 to
about 3,000, and more preferably within the range of about 900 to about
2,500 with approximately one terminal double bond per polymer chain. An
especially useful starting material for a highly potent dispersant
additive made in accordance with this invention is polyisobutylene. The
number average molecular weight for such polymers can be determined by
several known techniques. A convenient method for such determination is by
gel permeation chromatography (GPC) which additionally provides molecular
weight distribution information, see W. W. Yau, J. J. Kirkland and D. D.
Bly, "Moder Size Exclusion Liquid Chromatography", John Wiley and Sons,
New York, 1979.
Processes for substituting the hydroxy aromatic compounds with the olefin
polymer are known in the art and may be depicted as follows:
##STR12##
where R.sup.20, R.sup.21, y and x are as previously defined, and BF3 is an
alkylating catalyst. Processes of this type are described, for example, in
U.S. Pat. Nos. 3,539,633 and 3,649,229, the disclosures of which are
incorporated herein by reference.
Representative hydrocarbyl substituted hydroxy aromatic compounds
contemplated for use in the present invention include, but are not limited
to, 2-polypropylene phenol, 3-polypropylene phenol, 4-polypropylene
phenol, 2-polybutylene phenol, 3-polyisobutylene phenol, 4-polyisobutylene
phenol, 4-polyisobutylene-2-chlorophenol,
4-polyisobutylene-2-methylphenol, and the like.
Suitable hydrocarbyl-substituted polyhydroxy aromatic compounds include the
polyolefin catechols, the polyolefin resorcinols, and the polyolefin
hydroquinones, e . g., 4-polyisob utyle ne-1 ,2-dihydroxybenzene,
3-polypropylene-1,2-dihydroxyenzene,
5-polyisobutylene-1,3-dihydroxybenzene,
4-polyamylene-1,3-dihydroxybenzene, and the like.
Suitable hydrocarbyl-substituted naphthols include
1-polyisobutylene-5-hydroxynaphthalene, 1
polypropylene-3-hydroxynaphthalene and the like.
The preferred long chain hydrocarbyl substituted hydroxy aromatic compounds
to be used in this invention can be illustrated by the formula:
##STR13##
wherein R.sup.22 is hydrocar 1 of from 50 to 300 carbon atoms, and
preferably is a polyolefin derived from a C.sub.2 to C.sub.10 (e.g.,
C.sub.2 to C.sub.5) mono-alpha-olefin.
The aldehyde material which can be employed is represented by the formula:
R.sup.23 CHO
in which R.sup.23 is a hydrogen or an aliphatic hydrocarbon radical having
from 1 to 4 carbon atoms. Examples of suitable aldehydes include
formaldehyde, paraformaldehyde, acetaldehyde and the like.
The reaction scheme involving the reaction between the polyepoxide, e.g., a
diepoxide, and a polyamine which polyamine is present in excess e.g.,
TEPA, to form the intermediate adduct is represented by Equation 1. This
intermediate adduct is then reacted with the hydrocarbyl substituted
aromatic compound, e.g., polyisobutenyl substituted phenol, and an
aldehyde, e.g., formaldehyde, to form the dispersant of this embodiment as
follows:
##STR14##
POLYEPOXIDES
The polyepoxides are compounds containing at least two oxirane rings, i.e,
##STR15##
These oxirane rings are connected or joined by hydrocarbon or hydrocarbon
moieties containing at least one hetero atom or group. The hydrocarbon
moieties generally contain from 1 to about 100 carbon atoms. They include
the alkylene, cycloalkylene, alkenylene, arylene, aralkenylene and
alkarylene radicals Typical alkylene radicals are those containing from to
about 100 carbon atoms, more typically from 1 to about 50 carbon atoms.
The alkylene radicals may be straight chain or branched and may contain
from 1 to about 100 carbon atoms, preferably from 1 to about 50 carbon
atoms. Typical cycloalkylene radicals are those containing from 4 to about
16 ring carbon atoms. The cycloalkylene radicals may contain alkyl
substituents, e.g., C.sub.1 -C.sub.8 alkyl, on one or more ring carbon
atoms. Typical arylene radicals are those containing from 6 to 12 ring
carbons, e.g., phenylene, naphthylene and biphenylene. Typical alkarylene
and aralkylene radicals are these containing from 7 to about 100 carbon
atoms, preferably from 7 to about 50 carbon atoms. The hydrocarbon
moieties joining the oxirane rings may contain substituent groups thereon.
The substituent groups are those which are substantially inert or
unreactive at ambient conditions with the oxirane ring. As used in the
specification and appended claims the term "substantially inert and
unreactive at ambient conditions" is intended to mean that the atom or
group is substantially inert to chemical reactions at ambient temperatures
and pressure with the oxirane ring so as not to materially interfere in an
adverse manner with the preparation and/or functioning of the
compositions, additives, compounds, etc. of this invention in the context
of its intended use. For example, small amounts of these atoms or groups
can undergo minimal reaction with the oxirane ring without preventing the
making and using of the invention as described herein. In other words,
such reaction, while technically discernable, would not be sufficient to
deter the practical worker of ordinary skill in the art from making and
using the invention for its intended purposes. Suitable substituent groups
include, but are not limited to, alkyl groups, hydroxyl groups, tertiary
amino groups, halogens, and the like. When more than one substituent is
present they may be the same or different.
It is to be understood that while many substituent groups are substantially
inert or unreactive at ambient conditions with the oxirane ring, they will
react with the oxirane ring under conditions effective to allow reaction
of the oxirane ring with the reactive amino groups of the acylated
nitrogen derivatives of hydrocarbyl substituted dicarboxylic materials.
Whether these groups are suitable substituent groups which can be present
on the polyepoxide depends, in part, upon their reactivity with the
oxirane ring. Generally, if they are substantially more reactive with the
oxirane ring than the oxirane ring is with the reactive amino group,
particularly the secondary amino group, they will tend to materially
interfere in an adverse manner with the preparation of the improved
dispersants of this invention and are, therefore, unsuitable. If, however,
their reactivity with the oxirane ring is less than or generally similar
to the reactivity of the oxirane ring with the reactive amino groups,
particularly a secondary amino group, they will not materially interfere
in an adverse manner with the preparation of the dispersants of the
present invention and may be present on the polyepoxide, particularly if
the epoxide groups are present in excess relative to the substituent
groups. An example of such a reactive but suitable group is the hydroxyl
group. An example of an unsuitable substituent group is a primary amino
group.
The hydrocarbon moieties containing at least one hetero atom or group are
the hydrocarbon moieties described above which contain at least one hetero
atom or group in the chain. The hetero atoms or groups are those that are
substantially unreactive at ambient conditions with the oxirane rings.
When more then one hetero atom or group is present they may be the same or
different. The hetero atoms or groups are separated from the carbon atom
of the oxirane ring by at least one intervening carbon atom. These hetero
atom or group containing hydrocarbon moieties may contain at least one
substituent group on at least one carbon atom. These substituent groups
are the same as those described above as being suitable for the
hydrocarbon moieties.
Some illustrative non-limiting examples of suitable hetero atoms or groups
include:
##STR16##
As mentioned hereinafore the polyepoxides of the present invention contain
at least two oxirane rings or epoxide moieties. It is critical that the
polyepoxide contain at least two oxirane rings in the same molecule.
Preferably, these polyepoxides contain no more than about 10 oxirane
rings, preferably no more than about 5 oxirane rings. Preferred
polyepoxides are the diepoxides, i.e., those containing two oxirane rings.
The polyepoxides useful in the instant invention are well known in the art
and are generally commercially available or may readily be prepared by
conventional and well known methods.
The polyepoxides include those represented by the general formula
##STR17##
wherein:
R.sup.30 is as valent hydrocarbon radical, a substituted s valent
hydrocarbon radical, a s valent hydrocarbon radical containing at least
one hetero atom or group, and a substituted s valent hydrocarbon radical
containing at least one hetero atom or group; R.sup.1 -R.sup.3 are as
described herein below; and s is an integer having a value of at least 2,
preferably from 2 to about 10, more preferablly from 2 to about 5. In this
generic formula R.sup.30 has the same meaning as R in Formula V below
except that it is s valent rather than divalent.
Among the polyepoxides described hereinafore are those represented by the
general formula.
##STR18##
wherein:
R is a divalent hydrocarbon radical, a substituted divalent hydrocarbon
radical, a divalent hydrocarbon radical containing at least one hetero
atom or group, and a substituted divalent hydrocarbon radical containing
at least one hetero atom or group.;
R.sup.1 and R.sup.6 are independently selected from hydrogen, monovalent
hydrocarbon radicals, substituted monovalent hydrocarbon radicals,
monovalent hydrocarbon radicals containing at least one hetero atom or
group, substituted monovalent hydrocarbon radicals containing at least one
hetero atom or group, and oxirane containing radicals;
R.sup.2 and R.sup.3 are independently selected from hydrogen, monovalent
hydrocarbon radicals, substituted monovalent hydrocarbon radicals,
monovalent hydrocarbon radicals containing at least one hetero atom or
group, substituted monovalent hydrocarbon radicals containing at least one
hetero atom or group, monovalent oxirane containing radicals, divalent
hydrocarbon radicals, and substituted divalent hydrocarbon radicals, with
the proviso that if R.sup.2 or R.sup.3 is a divalent hydrocarbon radical
or substituted divalent hydrocarbon radical then both R.sup.2 and R.sup.3
must be divalent hydrocarbon radicals or substituted divalent hydrocarbon
radicals that together with the two carbon atoms of the oxirane ring form
a cyclic structure; and
R.sup.4 and R.sup.5 are independently selected from hydrogen, monovalent
hydrocarbon radicals, substituted monovalent hydrocarbon radicals,
monovalent hydrocarbon radicals containing at least one hetero atom or
group, substituted monovalent hydrocarbon radicals containing at least one
hetero atom or group, monovalent oxirane containing radicals, divalent
hydrocarbon radicals, and substituted divalent hydrocarbon radicals, with
the proviso that if R.sup.4 or R.sup.5 is a divalent hydrocarbon radical
or substituted divalent hydrocarbon radical then both R.sup.4 and R.sup.5
must be divalent hydrocarbon radicals or substituted divalent hydrocarbon
radicals that together with the two carbon atoms of the oxirane ring form
a cyclic structure.
The monovalent hydrocarbon radicals represented by R.sup.1 -R.sup.6
generally contain from to about 100 carbon atoms. These hydrocarbon
radicals include alkyl, alkenyl, cycloalkyl, aryl, aralkyl, and alkaryl
radicals. The alkyl radicals may contain from 1 to about 100, preferably
from 1 to about 50, carbon atoms and may be straight chain or branched.
The alkenyl radicals may contain from 2 to about 100 carbons, preferably
from 2 to about 50 carbon atoms, and may be straight chain or branched.
Preferred cycloalkyl radicals are those containing from about 4 to about
12 ring carbon atoms, e.g., cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, etc. These cycloalkyl radicals may contain substituent
groups, preferably alkyl groups, on the ring carbon atoms, e.g.,
methylcyclohexyl, 1,3-dimethylcyclopentyl, etc. The preferred alkenyl
radicals are those containing from 2 to about 30 carbon atoms, e.g.,
ethenyl, 1-propenyl, 2-propenyl, etc. The preferred aryl radicals are
those containing from 6 to about 12 ring carbon atoms, i.e., phenyl,
naphthyl, and biphenyl. The preferred aralkyl and alkaryl radicals are
those containing from 7 to about 30 carbon atoms, e.g., p-tolyl,
2,6-xylyl, 2,4,6-trimethylphenyl, 2-isopropylphenyl, benzyl,
2-phenylethyl, 4-phenylbutyl, etc.
The substituted monovalent hydrocarbon radicals represented by R.sup.1
-R.sup.6 are the monovalent hydrocarbon radicals described hereinafore
which contain at least one substituent group thereon. The substituent
groups are such that they are substantially unreactive under ambient
conditions with the oxirane moieties. When more than one substituent group
is present they may be the same or different.
The monovalent hydrocarbon radicals containing at least one hetero atom or
group are the monovalent hydrocarbon radicals described hereinafore which
contain at least one hetero atom or group in the carbon chain. The hetero
atom or group is separated from the carbon of the oxirane ring by at least
one intervening carbon atom. When more than one hetero atom or group is
present they may be the same or different. The hetero atoms or groups are
those that are substantially unreactive under ambient conditions with the
oxirane ring. These hetero atoms or groups are those described
hereinafore.
The substituted monovalent hydrocarbon radicals containing at least one
hetero atom or group are the substituted monovalent hydrocarbon radicals
containing at least one hetero atom or group described above which contain
at least one substituent group on at least one carbon atom. The
substituent groups are those described hereinafore.
The oxirane radicals represented by R.sup.1 -R.sup.6 may be represented by
the formula
##STR19##
wherein:
R.sup.7 has the same meaning as R.sup.1, R.sup.8 -R.sup.9 have the same
meaning as R.sup.2 R.sup.3, and RIO has the same meaning as R in Formula
V. The divalent hydrocarbon radicals represented by R.sup.2 -R.sup.5 and
R.sup.8 -R.sup.9 generally are aliphatic acrylic radicals and contain from
1 to about 5 carbon atoms. Preferred divalent hydrocarbon radicals are the
alkylene radicals. Preferred alkylene radicals are those that, together
with the two carbon atoms of the oxirane ring, form a cyclic structure
containing from 4 to about 8 ring carbon atoms. Thus, for example, if
R.sup.3 and R.sup.4 are both ethylene radicals the resultant cyclic
structure formed with the two carbon atoms of the oxirane ring is a
cyclohexylene oxide i.e.,
##STR20##
The divalent substituted hydrocarbon radicals represented by R.sup.2
-R.sup.5 and R.sup.8 -R.sup.9 are the divalent hydrocarbon radicals
described above which contain at least one substituent group on at least
one carbon atom. Thus, for example, if R.sup.3 and R.sup.4 are both
hydroxy substituted ethylene radicals, the resultant cyclic structure
formed with the two carbon atoms of the oxirane ring may be represented by
the formula.
##STR21##
The divalent hydrocarbon radicals represented by R and R.sup.10 generally
contain from to about 100 carbon atoms, preferably from 1 to about 50
carbon atoms. They may be aliphatic, aromatic or aliphatic-aromatic. If
they are aliphatic they may be saturated or unsaturated, acrylic or
alicyclic. They include alkylene, cycloalkylene, alkenylene, arylene,
aralkylene, and alkarylene radicals. The alkylene radicals may be straight
chain or branched. Preferred alkylene radicals are those containing from 1
to about 50 carbon atoms. Preferred alkenylene radicals are those
containing from 2 to about 50 carbon atoms. Preferred cycloalkylene
radicals are those containing from 4 to about 12 ring carbon atoms. The
cycloalkylene radicals may contain substituents, preferably alkyls, on the
ring carbon atoms.
It is to be understood that the term "arylene" as used in the specification
and the appended claims is not intended to limit the divalent aromatic
moiety represented by R and R10 to benzene. Accordingly, it is to be
understood that the divalent aromatic moiety can be a single aromatic
nucleus such as a benzene nucleus, a pyridine nucleus, a thiophene
nucleus, a 1,2,3,4-tetrahydronaphthalene nucleus, etc., or a polynuclear
aromatic moiety. Such polynuclear moieties can be of the fused type; that
is, wherein at least one aromatic nucleus is fused at two points to
another nucleus such as found in naphthalene, anthracene, the
azanaphthalenes, etc. Alternatively, such polynuclear aromatic moieties
can be of the linked type wherein at least two nuclei (either mono-or
polynuclear) are linked through bridging linkages to each other. Such
bridging linkages can be chosen from the group consisting of
carbon-to-carbon single bonds, ether linkages, keto linkages, sulfide
linkages, polysulfide linkages of 2 to 6 sulfur atoms, sulfinyl linkages,
sufonyl linkages, methylene linkages, alkylene linkages, di-(lower
alkyl)-methylene linkages, lower alkylene ether linkages, alkylene keto
linkages, lower alkylene sulfur linkages, lower alkylene polysulfide
linkages of 2 to 6 carbon atoms, amino linkages, polyamino linkages and
mixtures of such divalent bridging linkages.
When the divalent aromatic moiety, Ar, is a linked polynuclear aromatic
moiety it can be represented by the general formula
--Ar(Lng--Ar.sub.w)
wherein w is an integer of 1 to about 10, preferably 1 to about 8, more
preferably 1, 2 or 3; Ar is a divalent aromatic moiety as described above,
and each Lng is a bridging linkage individually chosen from the group
consisting of carbon-to-carbon single bonds, ether linkages (e.g. --0--),
keto linkages (e.g.,
##STR22##
sulfide linkages (e.g., --S--), polysulfide linkages of 2 to 6 sulfur
atoms (e.g., --S.sub.2 --), sulfinyl linkages (e.g., --S (0) -) sufonyl
linkages (e.g., ----S (0)2 --) lower alkylene linkages (e.g.,
##STR23##
di (lower alkyl) -methylene linkages (e.g., --CR.sup.* 2--), lower
alkylene ether linkages (e.g.,
##STR24##
etc.) lower alkylene sulfide linkages (e.g., wherein one or more -0--'s in
the lower alkylene ether linkages is replaced with an --S--atom), lower
alkylene polysulfide linkages (e.g., wherein one or more -0--'s is
replaced with a --S.sub.2 to --S.sub.6 --group), with R* being a lower
alkyl group.
Illustrative of such linked polynuclear aromatic moieties are those
represented by the formula
##STR25##
wherein R.sup.12 and R.sup.13 are independently selected from hydrogen and
alkyl radicals, preferably alkyl radicals containing from 1 to about 2 0
carbon atoms; R11 is selected from alkylene, alkylidene, cycloalkylene,
and cycloalkylidene radicals; and u and ul are independently selected from
integers having a value of from 1 to 4.
The divalent substituted hydrocarbon radicals represented by R and R10 are
those divalent hydrocarbon radicals described above which contain at least
one substituent group of the type described hereinafore. Thus, for
example, if the divalent hydrocarbon radical is a C.sub.5 alkylene, the
corresponding divalent substitute hydrocarbon radical, e.g., hydroxyl
substituted radical, may be
##STR26##
When more than one substituent group is present they may be the same or
different.
The divalent hydrocarbon radicals containing at least one hetero atom or
group are those divalent hydrocarbon radicals described hereinafore which
contain at least one hetero atom or group. These hetero atoms or groups
are those described hereinafore. Some illustrative non-limiting examples
of divalent hydrocarbon radicals containing at least one hetero atom or
group include:
##STR27##
the divalent substituted hydrocarbon radicals containing at least one
hetero atom or group are those divalent hydrocarbon radicals containing at
least one hetero atom or group described above which contain at least one
substitutent group of the type described hereinafore. Some illustrative
non-limiting examples of divalent substituted hydrocarbon radicals
containing at least one hetero atom or group include:
##STR28##
Also included within the scope of the polyepoxides of the instant invention
are these represented by the formula
##STR29##
wherein:
R and R.sup.1 -R.sup.3 are as defined hereinafore; R.sup.14 and R.sup.15
independently have the same meaning as R.sup.1 ; X is an aromatic moiety;
R.sup.16 and R.sup.17 are independently selected from divalent aliphatic
acrylic hydrocarbon radicals and divalent substituted aliphatic acrylic
hydrocarbon radicals which together with the two carbon atoms of the
oxirane ring and the two adjacent ring carbon atoms of the aromatic moiety
X form a cyclic structure;
m and m.sup.1 are independently zero or one with the proviso that the sum
of m plus m.sup.1 is at least one; and p is zero or one.
The aromatic moieties represented by X are preferably those containing from
6 to 12 ring carbon atoms, e.g., benzene, napthalene, and biphenyl. The
aromatic moieties may contain one or more substituents on one or more ring
carbon atoms. These substituents are those which are substantially
unreactive at ambient conditions, e.g., temperature and pressure, with the
oxirane ring. They include, for example, alkyl, hydroxyl, nitro, and the
like.
Also falling within the scope of the polyepoxides of the instant invention
are those represented by the formula:
##STR30##
wherein:
R', R.sup.1 -R.sup.3, R.sup.14 -R.sup.15 and p are as defined hereinafore;
and R.sup.18 is independently selected from divalent hydrocarbon radicals
or a substituted divalent hydrocarbon radicals which together with the two
carbon atoms of the oxirane ring forms a cyclic preferably cycloaliphatic,
structure.
The divalent hydrocarbon or substituted divalent hydrocarbon radicals
represented by R.sup.18 preferably contain from 2 to about 14 carbon atoms
so as to form, together with the two carbon atoms of the oxirane ring, a 4
to about 16 membered ring structure, preferably a cycloaliphatic ring. The
preferred divalent hydrocarbon radicals are the divalent aliphatic
hydrocarbon radicals, preferably the alkylene radicals.
The divalent aliphatic hydrocarbon radicals represented by R.sup.18 may
contain one or more substituent groups on one or more ring carbon atoms.
The substituents are selected from those that are substantially unreactive
under ambient conditions with the oxirane ring, e.g., alkyl, hydroxyl, and
the like.
Preferred polyepoxides of the instant invention are those wherein at least
two of the oxirane rings, preferably the two terminal or end oxirane
rings, are unhindered. By unhindered is meant that the oxirane ring
contains one secondary carbon atom, i.e., having two hydrogens bonded
thereto, and preferably contains one secondary carbon atom and one
tertiary carbon atom, i.e., having one hydrogen bonded thereto. Thus, for
example, an unhindered polyepoxide of Formula V is one wherein R.sup.1,
R.sup.2, R.sup.5, and R.sup.6 are hydrogen, preferably one wherein R.sup.1
-R.sup.3 and R.sup.4 -R.sup.6 are all hydrogen.
Some illustrative non-limiting Examples of the polyepoxides of the instant
invention include:
##STR31##
The polyepoxides useful in the instant invention also include the epoxy
resins. These epoxy resins are well known in the art and are generally
commercially available. They are described, for example, in billmeyer, F.
W. Jr., Textbook of Polymer Science, 2nd edition, Wiley-Interscience, N.Y.
1971, pp. 479-480; Lee, H and neville, K., "Epoxy Resins", pp. 209-271 in
Mark, H. f., Galylord, N. G. and Bikales, N. M., eds., Encyclopedia of
Polymer Science and Technology, Vol. 6, Interscience Div., John Wiley and
Sons, N.Y., 1967; and in U.S. Pat. Nos. 3,477,990 and 3,408,422; all of
which are incorporated herein by reference.
The epoxy resins (or polyepoxides) include those compounds possessing one
or more vicinal epoxy groups. These polyepoxides are saturated or
unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and are
substituted, if desired, with non-interfering substituents, such as
halogen atoms, hydroxyl groups, ether radicals, and the like.
Preferred polyepoxides are the glycidyl polyethers of polyhydric phenols
and polyhydric alcohols, especially the glycidyl polyethers of
2,2--bis(4--hydroxyphenyl) propane having an average molecular weight
between about 300 and 3,000 and an epoxide equivalent weight (WPE) between
about 140 and 2,000. Especially preferred are the diglycidyl polyethers of
2,2--bis(4--hydroxyphenyl) propane having a WPE between about 140 and 500
and an average molecular weight of from about 300 to about 900.
Other suitable epoxy compounds include those compounds derived from
polyhydric phenols and having at least one vicinal epoxy group wherein the
carbon-to-carbon bonds within the six-membered ring are saturated. Such
epoxy resins may be obtained by at least two well-known techniques, i.e.,
by the hydrogenation of glycidyl polyethers of polyhydric phenols or (2)
by the reaction of hydrogenated polyhydric phenols with epichlorohydrin in
the presence of a suitable catalyst such as Lewis acids, i.e., boron
trihalides and complexes thereof, and subsequent dehydrochlorination in an
alkaline medium. The method of preparation forms no part of the present
invention and the resulting saturated epoxy resins derived by either
method are suitable in the present compositions.
Briefly, the first method comprises the hydrogenation of glycidyl
polyethers of polyhydric phenols with hydrogen in the presence of a
catalyst consisting of rhodium and/or ruthenium supported on an inert
carrier at a temperature below about 50.degree. C. This method is
thoroughly disclosed and described in U.S. Pat. No. 3,336,241, issued Aug.
15, 1967.
The hydrogenated epoxy compounds prepared by the process disclosed in U.S.
Pat. No. 3,336,241 are suitable for use in the present compositions
Accordingly, the relevant disclosure of U.S. Pat. No. 3,336,241 is
incorporated herein by reference.
The second method comprises the condensation of a hydrogenated polyphenol
with an epihalohydrin, such as epichlorohydrin, in the presence of a
suitable catalyst such as BF3, followed by dehydrohalogenation in the
presence of caustic. When the phenol is hydrogenated Bisphenol A, the
resulting saturated epoxy compound is sometimes referred to as
"diepoxidized hydrogenated Bisphenol A," or more properly as the
diglycidyl ether of 2,2--bis(4--cyclohexanol) propane.
In any event, the term "saturated epoxy resin," as used herein shall be
deemed to mean the glycidyl ethers of polyhydric phenols wherein the
aromatic ring structure of the phenols have been or are saturated.
Preferred saturated epoxy resins are the hydrogenated resins prepared by
the process described in U.S. Pat. No. 3,336,241. More preferred are the
hydrogenated glylcidyl ethers of 2,2--bis(4--hydroxyphenyl) propane,
sometimes called the diglycidyl ethers of 2,2--bis(4--cyclohexanol)
propane.
One class of useful epoxy resins are those prepared by condensing
epichlorohydrin with bisphenol-A. They include resins represented by the
general structural formula
##STR32##
wherein:
R.sup.1 -R.sup.6 are defined hereinafore, and preferably are all hydrogen;
R.sup.20 is independently selected from alkyl radicals, preferably alkyl
radicals containing from to about 10 carbon atoms, hydroxyl, or halogen
radicals;
R.sup.21 is independently selected from alkyl radicals, preferably alkyl
radicals containing from 1 to about 10 carbon atoms, hydroxyl, or halogen
radicals;
v is independently selected from integers having a value of from 0 to 4
inclusive;
w is independently selected from integers having a value of from 0 to 4
inclusive; and
f has a value of at least one, and varies according to the molecular weight
of the resin, with the upper-limit of f preferably not exceeding about 10,
more preferably not exceeding about 5.
Preferred compounds of Formula X are those wherein R.sup.1 -R.sup.6 are all
hydrogen, and v and w are all zero.
An example of commercially available and useful epoxy resins are the EPON
resins of Shell Oil Company
As mentioned hereinafore those polyepoxides, including the epoxy reins,
wherein the two carbon atoms of the oxirane ring are bonded to three
hydrogen atoms, e.g., wherein R.sup.1 -R.sup.6 in Formula V are all
hydrogen, are preferred. Preferred polyepoxides of this type are those
wherein the hydrocarbon moieties bridging the epoxide moieties, e.g., R in
Formula V, contain polar groups or atoms. These polar groups or atoms
include, but are not limited to, the polar hetero atoms or groups
described hereinafore. Particularly preferred polyepoxides are the epoxy
resins, especially those devised from polyhydric phenols.
These polyepoxides are reacted with the polyamines, polyols or amino
alcohols described hereinafore to produce the intermediate adducts which
are then reacted with the aforedescribed acylating agents to yield the
dispersants of the present invention.
The reaction between a polyamine and a polyepoxide to form the intermediate
polyepoxide-polyamine adduct is described, for the case of a diepoxide, in
Equation 1 above. In this reaction the different oxirane moieties in the
same polyepoxide molecule react, by an oxirane ring opening mechanism,
with the primary amino groups on different polyamine molecules to join or
link together different polyamine molecules via the polyepoxide molecule.
If a polyepoxide containing more than two oxirane rings per molecule such
as a triepoxide is reacted with a polyamine such as TEPA in a 1: 3 mole
ratio then three molecules of polyamine will be linked or connected
together by the polyepoxide This is illustrated by the following reaction
scheme:
##STR33##
If a polyamine containing more than two, e.g., three, primary amino groups
per molecule is used then one such polyamine molecule may be linked or
connected to three other polyamine molecules by three diepoxide molecules.
In such case the three primary amino groups on each polyamine molecule
react with oxirane rings on different diepoxide molecules.
The chemistry of the polyepoxide-polyamine reaction is such that the
primary amino functionality in the polyamine is more reactive than the
secondary amino functionality with the oxirane ring of the polyepoxide and
therefore the product structure illustrated in Equations 1 and 2 will be
the favored product. It is also possible, however, that the secondary
amino functionality or the hydroxyl functionality of the resulting adduct
can react with further molecules of the polyepoxide to form a diversity of
structures.
In general the polyepoxide-polyamine intermediate adducts of the present
invention comprise molecules of polyamines linked to each other by
polyepoxide molecules. For purposes of illustration and exemplification
only, and assuming that the polyamine is a polyamine of Formula I and the
polyepoxide is a diepoxide of Formula V, the polyepoxide-polyamine
intermediate adduct contains at least one of the following recurring
structural units
##STR34##
wherein R, R'', R''', s and t are as defined hereinafore.
The stoichiometry of the polyepoxide and polyamine is one of the factors
that determines the length of the polyepoxide-polyamine adduct, e.g.,
number of recurring structural units of Formula X. Generally, increasing
the concentration in the reaction mixture of the polyepoxide, up to a
point where there is present an equivalent amount of oxirane ring moieties
per primary amino .moieties, results in an increase in the length and
molecular weight of the intermediate adduct.
Other factors which influence the length and molecular weight of the adduct
are reaction times and reaction temperatures and the presence or absence
of other reactive groups in the polyepoxide Generally, assuming a fixed
amount of polyepoxide in the polyepoxide-polyamine reaction mixture, a
higher reaction temperature and/or a longer reaction time results in
longer or higher molecular weight intermediate adduct product.
Reaction between the polyepoxide and polyamine is carried out by adding an
amount of polyepoxide to the polyamine which is effective to couple or
link at least some of the polyamine molecules. It is readily apparent to
those skilled in the art that the amount of polyepoxide utilized depends
upon a number of factors including (1) the number of primary amino groups
present in the polyamine, (2) the number of oxirane rings present in the
polyepoxide, (3) and the number of polyamines that it is desired to react,
i.e., the degree of coupling or chain length of the polyepoxide-polyamine
adduct it is desired to achieve. It is generally preferred that the
polyamine be present in excess in the polyepoxide-polyamine reaction
mixture.
Generally, however, it is preferred to utilize an amount of polyepoxide
such that there are present from about 0.01 to 10 equivalents of epoxide
groups per equivalent of primary amino groups, preferably from about 0.1
to 5 equivalents of epoxide groups per equivalent of primary amino group.
With appropriate variations to provide for the presence of hydroxyl groups
the aforedescribed method and discussion for the preparation of the
polyepoxide-polyamine intermediate adducts is also applicable to the
polyepoxide-polyol and polyepoxide-amino alcohol adducts.
In order to form the dispersants of the present invention the long chain
hydrocarbyl substituted dicarboxylic acid material or the aldehyde and
hydrocarbyl substituted hydroxy aromatic compound is reacted with a
polyepoxide-polyamine adduct, a polyepoxide-polyol adduct, a
polyepoxide-amino alcohol, or a mixture thereof. The amounts of
polyepoxide adduct and hydrocarbyl substituted dicarboxylic acid material
or the aldehyde and hydrocarbyl substituted hydroxy aromatic compound
utilized in this reaction are amounts which are effective to form the
dispersants of the instant invention, i.e., dispersant forming effective
amounts. It will be apparent to those skilled in the art that the amount
of polyepoxide adduct utilized will depend, in part, upon the number of
reactive groups (reactive primary and/or secondary amino groups and/or
hydroxy groups in the polyepoxide-polyamine adduct, reactive hydroxyl
groups in the polyepoxide-polyol adduct, etc.) present in said polyepoxide
adduct which are available for reaction with, for example, carboxylic acid
or anhydride groups of the hydrocarbyl substituted dicarboxylic acid
material. Generally, however, the amount of the polyepoxide adduct is such
that sufficient polyepoxide adduct is present to provide from about 0.5 to
15, preferably from about 1 to 10, and more preferably from about 2 to 4
reactive groups or equivalents, e.g., primary or secondary amino groups or
hydroxy groups, for each dicarboxylic acid or anhydride group or
equivalent present in the hydrocarbyl substituted dicarboxylic acid
material.
The reaction conditions under which the reaction between the polyepoxide
adduct and the hydrocarbyl substituted dicarboxylic acid material is
carried out are those that are effective for coreaction between said
polyepoxide adduct and the hydrocarbyl substituted dicarboxylic acid
material to occur. Generally, the reaction will proceed at from about
50.degree.. to 250.degree. C., preferably 100 to 210.degree. C. While
super-atmospheric pressures are not excluded, the reaction generally
proceeds satisfactorily at atmospheric pressure. The reaction may be
conducted using a mineral oil, e.g., 100 neutral oil, as a solvent An
inert organic co-solvent, e.g., xylene or toluene, may also be used. The
reaction time generally ranges from about 0.5-24 hours.
The reaction between the polyepoxide-polyamine adduct and the hydrocarbyl
substituted dicarboxylic acid material may be exemplified by the following
reaction scheme which represents the reaction of polyisobutenyl succinic
anhydride with an alkylene diepoxide/tetraethylene pentamine adduct:
##STR35##
The imide reaction product of this reaction may be represented by the
formula
##STR36##
where PIB is polyisobutylene.
Further aspects of the present invention reside in the formation of metal
complexes and other post-treatment derivatives, e.g., borated derivatives,
of the novel additives prepared in accordance with this invention.
Suitable metal complexes may be formed in accordance with known techniques
of employing a reactive metal ion species during or after the formation of
the present C.sub.5 -C.sub.9 lactone derived dispersant materials.
Complex-forming metal reactants include the nitrates, thiocyanates,
halides, carboxylates, phosphates, thio-phosphates sulfates, and borates
of transition metals such as iron, cobalt, nickel, copper, chromium,
manganese, molybdenum, tungsten, ruthenium, palladium, platinum, cadmium,
lead, silver, mercury, antimony and the like Prior art disclosures of
these complexing reactions may be found in U.S. Pat. Nos. 3,306,908 and
Re. 26,443.
Post-treatment compositions include those formed by reacting the novel
additives of the present invention with one or more post-treating
reagents, usually selected from the group consisting of boron oxide, boron
oxide hydrate, boron halides, boron acids, sulfur, sulfur chlorides,
phosphorous sulfides and oxides, carboxylic acid or anhydride acylating
agents, epoxides and episulfides and acrylonitriles. The reaction of such
post-treating agents with the novel additives of this invention is carried
out using procedures known in the art. For example, boration may be
accomplished in accordance with the teachings of U.S. Pat. No. 3,254,025
by treating the additive compound of the present invention with a boron
oxide, halide, ester or acid. Treatment may be carried out by adding about
1-3 wt. % of the boron compound, preferably boric acid, and heating and
stirring the reaction mixture at about 135.degree. C. to 165.degree. C.
for to 5 hours followed by nitrogen stripping and filtration, if desired.
Mineral oil or inert organic solvents facilitate the process.
The compositions produced in accordance with the present invention have
been found to be particularly useful as fuel and lubricating oil
additives.
When the compositions of this invention are used in normally liquid
petroleum fuels, such as middle distillates boiling from about 150 to
800.degree. F. including kerosene, diesel fuels, home heating fuel oil,
jet fuels, etc., a concentration of the additive in the fuel in the range
of typically from 0.001 wt. % to 0.5 wt. %, preferably 0.005 wt. % to 0.2
wt %, based on the total weight of the composition, will usually be
employed These additives can contribute fuel stability as well as
dispersant activity and/or varnish control behavior to the fuel.
The compounds of this invention find their primary utility, however, in
lubricating oil compositions, which employ a base oil in which the
additives are dissolved or dispersed. Such base oils may be natural or
synthetic.
Thus, base oils suitable for use in preparing the lubricating compositions
of the present invention include those conventionally employed as
crankcase lubricating oils for spark-ignited and compression-ignited
internal combustion engines, such as automobile and truck engines, marine
and railroad diesel engines, and the like. Advantageous results are also
achieved by employing the additives of the present invention in base oils
conventionally employed in and/or adapted for use as power transmitting
fluids such as automatic transmission fluids, tractor fluids, universal
tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power
steering fluids and the like Gear lubricants, industrial oils, pump oils
and other lubricating oil compositions can also benefit from the
incorporation therein of the additives of the present invention.
Thus, the additives of the present invention may be suitably incorporated
into synthetic base oils such as alkyl esters of dicarboxylic acids,
polyglycols and alcohols; polyalpha-olefins, polybutenes, alkyl benzenes,
organic esters of phosphoric acids, polysilicone oils, etc. selected type
of lubricating oil composition can be included as desired.
The additives of this invention are oil-soluble, dissolvable in oil with
the aid of a suitable solvent, or are stably dispersible materials.
Oil-soluble, dissolvable, or stably dispersible as that terminology is
used herein does not necessarily indicate that the materials are soluble,
dissolvable, miscible, or capable of being suspended in oil in all
proportions. It does mean, however, that the additives, for instance, are
soluble of stably dispersible in oil to an extent sufficient to exert
their intended effect in the environment in which the oil is employed
Moreover, the additional incorporation of other additives may also permit
incorporation of higher levels of a particular polymer adduct hereof, if
desired
Accordingly, while any effective amount of these additives can be
incorporated into the fully formulated lubricating oil composition, it is
contemplated that such effective amount be sufficient to provide said lube
oil composition with an amount of the additive of typically from 0.01 to
about 10, e.g., 0.1 to 6.0, and preferably from 0.25 to 3.0 wt. %, based
on the weight of said composition.
The additives of the present invention can be incorporated into the
lubricating oil in any convenient way. Thus, they can be added directly to
the oil by dispersing, or dissolving the same in the oil at the desired
level of concentration, typically with the aid of a suitable solvent such
as toluene, cyclohexane, or tetrahydrofuran. Such blending can occur at
room temperature or elevated.
Natural base oils include mineral lubricating oils which may vary widely as
to their crude source, e.g., whether paraffinic, naphthenic, mixed,
paraffinicnaphthenic, and the like; as well as to their formation, e.g.,
distillation range, straight run or cracked, hydrofined, solvent extracted
and the like.
More specifically, the natural lubricating oil base stocks which can be
used in the compositions of this invention may be straight mineral
lubricating oil or distillates derived from paraffinic, naphthenic,
asphaltic, or mixed base crudes, or, if desired, various blends oils may
be employed as well as residuals, particularly those from which asphaltic
constituents have been removed. The oils may be refined by conventional
methods using acid, alkali, and/or clay or other agents such as aluminum
chloride, or they may be extracted oils produced, for example, by solvent
extraction with solvents of the type of phenol, sulfur dioxide, furfural,
dichlorodiethyl ether, nitrobenzene, crotonaldehyde, etc.
The lubricating oil base stock conveniently has a viscosity of typically
about 2.5 to about 12, and preferably about 2.5 to about 9 cSt. at
100.degree. C.
Thus, the additives of the present invention can be employed in a
lubricating oil composition which comprises lubricating oil, typically in
a major amount, and the additive, typically in a minor amount, which is
effective to impart enhanced dispersancy relative to the absence of the
additive. Additional conventional additives selected to meet the
particular requirements of a temperatures. In this form the additive per
se is thus being utilized as a 100% active ingredient form which can 1
added to the oil or fuel formulation by the purchase: oil-soluble solvent
and base oil to form concentrate, which may then be blended with a
lubricating oil base stock to obtain the final formulation Concentrates
will typically contain from about 2 to 80 wt. %, by weight of the
additive, and preferably from about 5 to 40% by weight of the additive.
The lubricating oil base stock for the additive of the present invention
typically is adapted to perform selected function by the incorporation of
additives therein to form lubricating oil compositions (i.e.,
formulations).
Representative additives typically present in such formulation include
viscosity modifiers, corrosion inhibitors, oxidation inhibitors, friction
modifiers, other dispersants, anti-foaming agents, anti-wear agents, pour
point depressants, detergents, rust inhibitors and the like.
Viscosity modifiers impart high and low temperature operability to the
lubricating oil and permit it to remain shear stable at elevated
temperatures and also exhibit acceptable viscosity or fluidity at low
temperatures. These viscosity modifiers are generally high molecular
weight hydrocarbon polymers including polyesters. The viscosity modifiers
may also be derivatized to include other properties or functions, such as
the addition of dispersancy properties.
These oil soluble viscosity modifying polymers will generally have weight
average molecular weights of from about 10,000 to 1,000,000, preferably
20,000 to 500,000, as determined by gel permeation chromatography or light
scattering methods.
Representative examples of suitable viscosity modifiers are any of the
types known to the art including polyisobutylene, copolymers of ethylene
and propylene, polymethacrylates, methacrylate copolymers, copolymers of
an unsaturated dicarboxylic acid and vinyl compound, interpolymers of
styrene and acrylic esters, and partially hydrogenated copolymers of
styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as
the partially hydrogenated homopolymers of butadiene and isoprene.
Corrosion inhibitors, also known as anti-corrosive agents, reduce the
degradation of the metallic parts contacted by the lubricating oil
composition. Illustrative of corrosion inhibitors are phosphosulfurized
hydrocarbons and the products obtained by reaction of a phosphosulfurized
hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in
the presence of an alkylated phenol or of an alkylphenol thioester, and
also preferably in the presence of an alkylated phenol or of an
alkylphenol thioester, and also preferably in the presence of carbon
dioxide. Phosphosulfurized hydrocarbons are prepared by reacting a
suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a
C.sub.2 to C.sub.6 olefin polymer such as polyisobutylene, with from to 5
to 30 wt. % of a sulfide of phosphorus for 1/2 to 15 hours, at temperature
in the range of about 66 to about 316.degree. C. Neutralization of the
phosphosulfurized hydrocarbon may be effected in the manner taught in U S.
Pat. No. 1,969,324.
Oxidation inhibitors, or antioxidants, reduce the tendency of mineral oils
to deteriorate in service which deterioration can be evidenced by the
products of oxidation such as sludge and varnish-like deposits on the
metal surfaces, and by viscosity growth. Such oxidation inhibitors include
alkaline earth metal salts of alkyl-phenolthioesters having preferably
C.sub.5 to C.sub.12 alkyl side chains, e g calcium nonylphenol sulfide,
barium toctylphenyl sulfide, dioctylphenylamine, phenylalphanaphthylamine,
phospho-sulfurized or sulfurized hydrocarbons, etc.
Other oxidation inhibitors or antioxidants useful in this invention
comprise oil-soluble copper compounds. The copper may be blended into the
oil as any suitable oilsoluble copper compound By oil soluble it is meant
that the compound is oil soluble under normal blending conditions in the
oil or additive package. The copper compound may be in the cuprous or
cupric form. The copper may be in the form of the copper dihydrocarbyl
thio- or dithio-phosohates. Alternatively, the copper may be added as the
copper salt of a synthetic or natural carboxylic acid Examples of same
thus include C.sub.10 to C.sub.18 fatty acids, such as stearic or palmitic
acid, but unsaturated acids such as oleic or branched carboxylic acids
such as napthenic acids of molecular weights of from about 200 to 500, or
synthetic carboxylic acids, are preferred, because of the improved
handling and solubility properties of the resulting copper carboxylates
Also useful are oil-soluble copper dithiocarbamates of the general formula
(R.sup.20 R.sup.21, NCSS) zCu (where z is 1 or 2, and R.sup.20 and
R.sup.21, are the same or different hydrocarbyl radicals containing from 1
to 18, and preferably 2 to 12, carbon atoms, and including radicals such
as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals
Particularly preferred as R.sup.20 and R.sup.21, groups are alkyl groups
of from 2 to 8 carbon atoms. Thus, the radicals may, for example, be
ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl,
i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl,
phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl,
etc. In order to obtain oil solubility, the total number of carbon atoms
(i.e., R.sup.20 and R.sup.21, ) will generally by about 5 or greater.
Copper sulphonates, phenates, and acetylacetonates may also be used.
Exemplary of useful copper compounds are copper CuI and/or CuII salts of
alkenyl succinic acids or anhydrides The salts themselves may be basic,
neutral or acidic. They may be formed by reacting (a) polyalkylene
succinimides (having polymer groups of of 700 to 5,000) derived from
polyalkylene-polyamines, which have at least one free carboxylic acid
group, with (b) a reactive metal compound Suitable rective metal compounds
include those such as cupric or cuprous hydroxides, oxides, acetates,
borates, and carbonates or basic copper carbonate.
Examples of these metal salts are Cu salts of polyisobutenyl succinic
anhydride, and Cu salts of polyisobutenyl succinic acid. Preferably, the
selected metal employed is its divalent form, e.g., Cu+2.degree.. The
preferred substrates are polyalkenyl succinic acids in which the alkenyl
group has a molecular weight greater than about 700. The alkenyl group
desirably has a M.sub.n from about 900 to 1,400, and up to 2,500, with a
M.sub.n of about 950 being most preferred. Especially preferred is
polyisobutylene succinic anhydride or acid. These materials may desirably
be dissolved in a solvent, such as a mineral oil, and heated in the
presence of a water solution (or slurry) of the metal bearing material.
Heating may take place between 70.degree. C. and about 200.degree. C.
Temperatures of 100.degree. C. to 140.degree. C. are entirely adequate It
may be necessary, depending upon the salt produced, not to allow the
reaction to remain at a temperature above about 140.degree. C. for an
extended period of time, e.g., longer than 5 hours, or decomposition of
the salt may occur.
The copper antioxidants (e.g , Cu-polyisobutenyl succinic anhydride,
Cu-oleate, or mixtures thereof) will be generally employed in an amount of
from about 50 to 500 ppm by weight of the metal, in the final lubricating
or fuel composition.
Friction modifiers serve to impart the proper friction characteristics to
lubricating oil compositions such as automatic transmission fluids.
Representative examples of suitable friction modifiers are found in U.S.
Pat. No. 3,933,659 which discloses fatty acid esters and amides; U.S. Pat.
No. 4,176,074 which describes molybdenum complexes of polyisobutyenyl
succinic anhydride-amino alkanols; U.S. Pat. No. 4,105,571 Which discloses
glycerol esters of dimerized fatty acids; U S Pat. No. 3,779,928 which
disclosed alkane phosphonic acid salts; U.S. Pat. No. 3,778,375 which
discloses reaction products of a phosphonate with an oleamide; U.S. Pat.
No. 3,852,205 which discloses S-carboxyalkylene hydrocarbyl succinimide,
S-carboxyalkylene hydrocarbyl succinalic acid and mixtures therefore U.S.
Pat. No. 3,932,290 which discloses reaction products of di- (lower alkyl)
phosphites and epoxides; and U.S. Pat. No. 4,028,258 which discloses the
alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenyl
succinimides. The disclosures of the above references are herein
incorporated by reference The most preferred friction modifiers are
succinate esters, or metal salts thereof, of hydrocarbyl substituted
succinic acids or anhydrides and thiobis-alkanols such as described in
U.S. Pat. No. 4,344,853.
Dispersants maintain oil insolubles, resulting from oxidation during use,
in suspension in the fluid thus preventing sludge flocculation and
precipitation or deposition on metal parts. Suitable dispersants include
high molecular weight alkyl succinimides, the reaction product of
oil-soluble polyisobutylene succinic anhydride with ethylene amines such
as tetraethylene pentamine and borated salts thereof.
Pour point depressants, otherwise known as lube oil flow improvers, lower
the temperature at which the fluid will flow or can be poured. Such
additives are well known Typically of those additives which usefully
optimize the low temperature fluidity of the fluid are C.sub.8 -C.sub.18
dialkylfumarate vinyl acetate copolymers, polymethacrylates, and wax
naphthalene. Foam control can be provided by an antifoamant of the
polysiloxane type, e.g., silicone oil and polydimethyl siloxane.
Anti-wear agents, as their name implies, reduce wear of metal parts.
Representatives of conventional antiwear agents are zinc
dialkyldithiophosphate and zinc diaryldithiosphate.
Detergents and metal rust inhibitors include the metal salts of sulphonic
acids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates,
naphthenates and other oil soluble mono- and di-carboxylic acids. Highly
basic (viz. overbased) metal sales, such as highly basic alkaline earth
metal sulfonates (especially Ca and Mg salts) are frequently used as
detergents. Representative examples of such materials, and their methods
of preparation, are found in co-pending Ser. No. 754,001, filed July 11,
1985, the disclosure of which is hereby incorporated by reference.
Some of these numerous additives can provide a multiplicity of effects, e g
, a dispersant-oxidation inhibitor. This approach is well known and need
not be further elaborated herein.
Compositions when containing these conventional additives are typically
blended into the base oil in amounts which are effective to provide their
normal attendant function. Representative effective amounts of such
additives are illustrated as follows:
______________________________________
Wt % a.i. Wt. % a.i.
Additive (Broad) (Preferred)
______________________________________
Viscosity Modifier
.01-12 .01-4
Corrosion Inhibitor
.01-5 .01-1.5
Oxidation Inhibitor
.01-5 .01-1.5
Dispersant .1-20 .1-8
Pour Point Depressant
.01-5 .01-1.5
Anti-Foaming Agents
.001-3 .001-0.15
Anti-Wear Agents .001-5 .001-1.5
Friction Modifiers
.01-5 .01-1.5
Detergents/Rust Inhibitor
.01-10 .01-3
Mineral Oil Base Balance Balance
______________________________________
PG,60
When other additives are employed it may be desirable, although not
necessary, to prepare additive concentrates comprising concentrated
solutions or dispersions of the dispersant (in concentrate amounts
hereinabove described), together with one or more of said other additives
(said concentrate when constituting an additive mixture being referred to
herein as an additive package) whereby several additives can be added
simultaneously to the base oil to form the lubricating oil composition.
Dissolution of the additive concentrate into the lubricating oil may be
facilitated by solvents and by mixing accompanied with mild heating, but
this is not essential. The concentrate or additive-package will typically
by formulated to contain the dispersant additive and optional additional
additives in proper amounts to provide the desired concentration in the
final formulation when the additive-package is combined with a
predetermined amount of base lubricant Thus, the products of the present
invention can be added to small amounts of base oil or other compatible
solvents along with other desirable additives to form additive-packages
containing active ingredients in collective amounts of typically from
about 2.5 to about 90%, and preferably from about 5 to about 75%, and most
preferably from about 8 to about 50% by weight additives in the
appropriate proportions with the remainder being base oil.
The final formulations may employ typically about 10 wt. % of the
additive-package with the remainder being base oil.
All of said weight percents expressed herein are based on active ingredient
(a.i.) content of the additive, and/or upon the total weight of any
additive-package, or formulation which will be the sum of the a.i. weight
of each additive plus the weight of total oil or diluent.
This invention will be further understood by reference to the following
examples, wherein all parts are parts by weight and all molecular weights
are number weight average molecular weights as noted, and which include
preferred embodiments of the invention.
The following example illustrates a dispersant of the instant invention.
EXAMPLE 1
Into a reactor vessel are charged, under a nitrogen blanket and with
stirring, 100 grams of S150NR mineral oil, 25.8 grams of aminoethyl
piperazine and 17.4 (0.1 mole) grams of ethylene glycol diglycidyl ether.
This mixture is permitted to react for one hour at 20.degree.-60.degree.
C., after which reaction period 200 grams of polybutene succinic anhydride
(reaction product of maleic anhydride and polybutene having a of 950, said
reaction product having a polybutene to succinic anhydride ratio of about
1:1) are added over a 10-minute period. The resultant reaction mixture is
heated at 149.degree. C. and sparged with nitrogen for one-half hour. The
residue is diluted further with 15.55 grams of S150NR mineral oil per
81.45 grams of residue to yield a solution of the dispersant having a
viscosity at 100.degree. C. of 242.5 centistokes.
The following example illustrates a dispersant falling outside the scope of
the instant invention in that no polyepoxide is utilized in the
preparation of this dispersant. This example is presented for comparative
purposes only.
COMPARATIVE EXAMPLE 2
The procedure of Example 1 is substantially repeated, utilizing the same
ratios of S150NR mineral oil, and aminoethyl piperazine and polybutene
succinic anhydride reactants as in Example 1, with the exception that no
ethylene glycoldiglycidyl ether is present during the reaction. The oil
solution of the residue, which residue is diluted with S150NR mineral oil
to substantially the same degree as the residue of Example 1, has a
viscosity at 100.degree. C. of 76.3 centistokes
The higher viscosity of the oil solution of the residuc of Example 1 is
indicative of the fact that the polyepoxide reactant of Example 1 is
effective in increasing the molecular weight of the dispersant.
Top